JP2000035663A - Photosensitive composition and photosensitive lithographic printing plate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive composition small in occurrence of residual dyes and color stains in nonimage parts at the time of development processing by incorporating at least one kind of compound selected from specified compounds. SOLUTION: This photosensitive composition contains at least one kind of compound selected from the compound represented the formulae; R1(PO(OH)2)n and R1(PO(OH)(R2))n in which (n) is 1 or 2, and when it is 1, each of R1 and R2 is an optionally substituted alkyl, alkoxy, aryloxy, aryl, acyl, or acyloxy group, and when (n) is 2, R1 is an optionally substituted alkylene or arylene group and R2 is an alkyl, alkoxy, aryloxy, aryl, acyl, or acyloxy group. The compounds represented by the formulae may be the forms of the salts, such as K, Na, Li, or the like alkali metal salts, and Ca, Co, Fe, Ni, and Mn, and the like salts.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a photosensitive composition and a photosensitive lithographic printing plate.

[0002]

2. Description of the Related Art Conventionally, a lithographic printing plate is obtained by developing a photosensitive lithographic printing plate obtained by coating a photosensitive composition in a thin layer on an aluminum plate after image exposure. The above aluminum plate is usually subjected to a surface roughening treatment such as a mechanical method such as a brush grain method or a ball grain method, an electrochemical method such as an electrolytic grain method, or a method combining the both,
After the surface is pear-skinned, the surface is etched with an aqueous solution of an acid or an alkali, and further subjected to an anodizing treatment and, if desired, subjected to a hydrophilic treatment to form a support for a lithographic printing plate. A photosensitive lithographic printing plate (so-called PS plate) is provided with a photosensitive layer. This PS plate is usually subjected to image exposure, development, correction and gumming steps to form a lithographic printing plate, which is mounted on a printing machine for printing.

However, in the above lithographic printing plate,
Substances contained in the photosensitive layer are irreversibly adsorbed on the non-image areas of the lithographic printing plate obtained by image exposure and development, and contaminate the non-image areas, so-called residual colors are generated and the image is removed in the correction process. There is a problem that it is difficult to discriminate a portion from a non-image portion, or an erase (correction) mark is clearly left, resulting in a non-uniform plate surface. If the degree is too great, the outline becomes dirty and cannot be used as a printing plate. Was.

In order to improve this, a method of adding a cyclic acid anhydride described in US Pat. No. 4,115,128 to a photosensitive composition has heretofore been disclosed in JP-A-60-8.
JP-A No. 8942 and JP-A-2-96755 disclose methods of adding organic acids, which are used for the purpose of increasing sensitivity or increasing solubility in a developing solution. Therefore, the reduction of the residual color in the non-image area, which is the object of the present invention, is insufficient,
It was not satisfactory because there was a problem such as the occurrence of blemishes could not be completely suppressed, or the adhesion between the photosensitive composition and the support was insufficient, and the printing durability was significantly reduced. .

Further, a method of immersing an anodized aluminum support surface in an alkali metal silicate as described in US Pat. No. 3,181,461, US Pat. No. 3,860,426 -Priming hydrophilic cellulose containing water-soluble metal salts, as described in U.S. Pat. No. 5,098,056, or undercoating with sodium arylsulfonate as described in GB 2,098,627. US Patent No. 3,51,51
No. 1,661, polyacrylamide, Japanese Patent Publication No. 46-35885, polyvinyl phosphonic acid, Japanese Patent Application Laid-Open No. 60-149491, amino acids and salts thereof (Na salt) , K
Alkali metal salts such as salts, ammonium salts, hydrochlorides, oxalates, acetates, phosphates, etc.), JP-A-60-232998
Nos. 3,087,067 and 5,887,098. Amines having hydroxyl groups and their salts (hydrochloride, oxalate, phosphate, etc.) disclosed in
A method of undercoating a compound having an amino group and a phosphonic acid group or a salt thereof disclosed in JP-A-165183 is proposed. However, in these methods, the residual color in the non-image area is insufficiently reduced, the generation of the above-mentioned “stain” cannot be completely suppressed, or the adhesion between the photosensitive composition and the support is insufficient. In order to be sufficient, there were problems such as a significant decrease in printing durability, which was not satisfactory.

[0006]

SUMMARY OF THE INVENTION It is an object of the present invention to provide an image forming apparatus which does not previously undergo a hydrophilic treatment as described above, but which is subjected to image exposure and development to obtain a color residue (a non-image portion). An object of the present invention is to provide a photosensitive composition and a photosensitive lithographic printing plate which are less likely to cause stains (so-called residual colors). Still another object is to provide a photosensitive composition and a photosensitive lithographic printing plate in which an image portion is firmly adhered to a support to give a lithographic printing plate having excellent printing durability.

[0007]

The above objects of the present invention have been attained by the following constitutions.

(1) The following general formula (I) or general formula (I
A photosensitive composition comprising at least one compound selected from the compounds represented by I).

Formula (I) R ¹ (PO (OH) ₂ ) _n Formula (II) R ¹ (PO (OH) (R ² )) _n [wherein n is 1 or 2, and n is When 1, R ¹ ,
R ² is a substituted or unsubstituted alkyl group, alkoxy group,
Represents an aryloxy group, an aryl group, an acyl group, or an acyloxy group; when n is 2, R ¹ represents a substituted or unsubstituted alkylene group or an arylene group; and R ² represents a substituted or unsubstituted alkyl group, an alkoxy group, an aryloxy group. Represents an aryl group, an acyl group, or an acyloxy group. (2) The compound represented by the general formula (I) or (II) is contained in an amount of 0.1 to 20% by weight based on the photosensitive composition, and is represented by the following general formula (1). A photosensitive composition comprising an alkali-soluble resin having a structural unit in its molecular structure, and an o-quinonediazide compound.

[0010]

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Wherein R ₁ and R ₂ are hydrogen, alkyl or carboxyl, R ₃ is hydrogen, halogen or alkyl, R ₄ is hydrogen, alkyl, phenyl or aralkyl, A Represents a divalent organic group linking a nitrogen atom and an aromatic ring carbon atom, m represents 0 or 1, and B represents a phenylene group which may have a substituent or a naphthylene group which may have a substituent. (3) It is characterized in that the compound represented by the general formula (I) or (II) is contained in an amount of 0.1 to 20% by weight with respect to the photosensitive composition, and further contains an infrared absorbent. 2. The photosensitive composition according to the above 1, wherein

(4) A surface roughening treatment, followed by anodic oxidation, is applied to an aluminum support having an anodic oxide film layer of 1.0 g / m ² or more. A photosensitive lithographic printing plate comprising a photosensitive composition.

The present invention will be described in more detail. The compound represented by the general formula (I) or the general formula (II) of the present invention is a substituted or unsubstituted aliphatic compound or aromatic compound. When n is 1, R ¹ and R ² each represent a substituted or unsubstituted alkyl group (preferably having 1 to 14 carbon atoms), an alkoxy group (preferably having 1 to 14 carbon atoms), an aryloxy group ( It preferably has 6 to 10 carbon atoms, an aryl group (preferably 6 to 10 carbon atoms), an acyl group (preferably 1 to 14 carbon atoms), and an acyloxy group (preferably 1 to 14 carbon atoms). And when n is 2, R ¹ represents an alkylene group (preferably having 1 to 14 carbon atoms) or an arylene group (preferably having 6 to 10 carbon atoms).
R ² is as defined above, and the substituent is an alkyl group (limited to a substituent for an aryl residue), an aryl group (limited to a substituent for an alkyl residue), Examples include at least one selected from an alkoxy group, an acyl group, an acyloxy group, an aryloxy group, a vinyl group, a hydroxyl group, a carboxyl group, a cyano group, a nitro group, and a halogen atom.

As the aryloxy group, a phenoxy group,
A p-chlorophenoxy group, a p-methylphenoxy group, a pyridinyl group, and an aryl group include a phenyl group, an o-tolyl group, an m-tolyl group, a p-tolyl group, a p-chlorophenyl group, and an acyl group include a formyl group. , Acetyl group,
Examples of the propionyl group, benzoyl group, and acyloxy group include an acetoxy group, a propionyloxy group, and a pivaloyloxy group.

The compound represented by the formula (I) or (II) may be used in the form of a salt. As salts, besides alkali metal salts such as potassium, sodium and lithium,
Salts of calcium, cobalt, iron, nickel, manganese, magnesium, barium, copper and the like can be mentioned.

A specific example will be described below. Examples of the compound of the general formula (I) include phenylphosphonic acid, phenylphosphoric acid, naphthylphosphonic acid, naphthylphosphoric acid, glycerophosphonic acid, glycerophosphoric acid, p-nitrophenylphosphonic acid, p-nitrophenylphosphoric acid and p-nitrophenylphosphoric acid. Methoxyphenylphosphonic acid, p-methoxyphenylphosphoric acid, p-hydroxyphenylphosphonic acid, p-hydroxyphenylphosphoric acid, p-tolylphosphonic acid, p-tolylphosphoric acid, p-
Acetylphenylphosphonic acid, p-acetylphenylphosphoric acid, p-cyanophenylphosphonic acid, p-cyanophenylphosphoric acid, m-chlorophenylphosphonic acid, m-chlorophenylphosphoric acid, methylphosphonic acid, methylenediphosphonic acid, ethylphosphon Acid, ethylene diphosphonic acid, 2
-Carboxyethylphosphonic acid, phosphonoacetic acid, 2-phenylethylphosphonic acid, 2-hydroxyethylphosphonic acid, 1-hydroxyethane-
1,1-diphosphonic acid, aminohexyl phosphoric acid, 2-methoxyethylphosphonic acid, 2-acetylethylphosphonic acid, glycine-N, N-bis (methylenephosphonic acid), phosphoserine, phosphothreonine, pyridoxal phosphate and the like No.

Examples of the compounds of the general formula (II) include phenylphosphinic acid, naphthylphosphinic acid, diphenylphosphinic acid, dimethylphosphinic acid, p-nitrophenylphosphinic acid, p-methoxyphenylphosphinic acid, p-hydroxyphenylphosphine Acid, p-tolylphosphinic acid, p-acetylphenylphosphinic acid, bisnitrophenylphosphoric acid, dioctyl phosphate, diisopropyl phosphate, dibutyl phosphate, dimethyl phosphate, diethyl phosphate, di-2-phosphate
Ethylhexyl ester, phosphoric acid diphenyl ester,
Methylphosphinic acid, ethylphosphinic acid, diethylphosphinic acid, 2-carboxyethylphosphinic acid, 2-
Examples include phenylethylphosphinic acid, 2-hydroxyethylphosphinic acid, 2-methoxyethylphosphinic acid, and 2-acetylethylphosphinic acid.

These compounds may be used in combination of two or more. Particularly preferred compounds among these are phenylphosphonic acid, phenylphosphoric acid, naphthylphosphonic acid,
Examples include naphthylphosphoric acid, phenylphosphinic acid, diphenylphosphinic acid, and naphthylphosphinic acid.

The high molecular compound having a structural unit represented by the general formula (1) in the molecular structure of the present invention (hereinafter, referred to as "high molecular compound A") is non-photosensitive and has the above general formula (1) in the molecular structure. It is characterized by having a structural unit represented by (1), and has a homopolymer type having a repeating structure of only the structural unit or an unsaturated double bond between the structural unit and another vinyl monomer. It has a copolymer type structure having a repeating structure obtained by combining at least one structural unit represented by the structure. Examples of the structural unit used in combination with the structural unit represented by the general formula in the polymer compound of the present invention having a copolymer type structure, for example,
Ethylene, propylene, isobutylene, butadiene, ethylenically unsaturated olefins such as isoprene, for example,
Styrene, α-methylstyrene, p-methylstyrene,
Styrenes such as p-chlorostyrene, for example, acrylic acids such as acrylic acid and methacrylic acid, for example, unsaturated aliphatic dicarboxylic acids such as itaconic acid, maleic acid and maleic anhydride, for example, methyl acrylate, ethyl acrylate Α-methylene such as n-butyl acrylate, isobutyl acrylate, dodecyl acrylate, 2-chloroethyl acrylate, phenyl acrylate, methyl α-chloroacrylate, methyl methacrylate, ethyl methacrylate, ethyl ethacrylate Esters of aliphatic monocarboxylic acids, for example, nitriles such as acrylonitrile and methacrylonitrile, for example, amides such as acrylamide, for example, acrylanilide, p-chloroacrylanilide, m-nitroacrylanilide, m-methoxyacrylanilide etc Anilides, for example, vinyl acetate, vinyl propionate, vinyl benzoate, vinyl acetate and other vinyl esters, for example, vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, isobutyl vinyl ether, β-chloroethyl vinyl ether, vinyl chloride, vinylidene Chloride, vinylidene cyanide, for example, 1-methyl-1-methoxyethylene, 1,1-dimethoxyethylene, 1,2-dimethoxyethylene, 1,1-dimethoxycarbonylethylene,
Ethylene derivatives such as -methyl-1-nitroethylene,
For example, N-vinyl pyrrole, N-vinyl carbazole, N-vinyl indole, N-vinyl pyrrolidene, N
N-vinyl monomers such as vinylpyrrolidone. These monomers are present in the polymer compound in a structure in which the unsaturated double bond is cleaved.

Of the above-mentioned monomers, esters and nitriles of aliphatic monocarboxylic acids exhibit excellent performance for the purpose of the present invention and are preferred.

These monomers may be bonded to the molecular structure of the polymer compound A in either a block or random state.

In the structural unit of the polymer compound A represented by the general formula (1), B represents a phenylene group which may have a substituent or a naphthylene group which may have a substituent.
Since the characteristics of the photosensitive composition of the present invention are hardly greatly affected by the type of the substituent, any group can be used as the substituent. Representative substituents include, for example, alkyl groups, alkoxy groups, halogen atoms, acyl groups, hydroxyl groups, carboxyl groups, sulfonic groups, cyano groups, nitro groups, and the like. Next, typical specific examples of the polymer compound A will be described. In the following exemplified compounds, Mn is an average molecular weight, j, k, l, m and n.
Represents mol% of each structural unit.

[0023]

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[0024]

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[0025]

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[0026]

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[0027]

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The polymer compound A is synthesized as follows. That is, α · β-unsaturated acid chlorides or α · β
A first having unsaturated acid anhydrides and a phenolic hydroxyl group;
After reacting a secondary or secondary amine with a basic catalyst, if necessary, to synthesize a monomer having a structure corresponding to the structural unit represented by the above general formula, The polymer compound of the present invention can be obtained by homopolymerizing according to the method or copolymerizing the monomer with at least one of other vinyl monomers. On this occasion,
The molecular weight and the molar ratio of each structural unit can be obtained as an arbitrary value over a wide range by changing the charged molar ratio of each monomer and polymerization conditions in various ways. In order to effectively provide good small dot reproducibility when printing under severe printing conditions at high speeds, the molecular weight should be about 3500 to 100000, and the molar content of the structural unit represented by the above general formula should be at least 1
It is desirably 0 mol%.

As a typical example of the o-quinonediazide compound contained in the photosensitive composition, an o-naphthoquinonediazide compound can be mentioned. As the o-naphthoquinonediazide compound, an ester of 1,2-diazonaphthoquinonesulfonic acid and a pyrogallol-acetone resin described in JP-B-43-28403 is preferable. No. 3,046, U.S. Pat.
No. 120, 3,188,210, esters of 1,2-diazonaphthoquinone-5-sulfonic acid with phenol / formaldehyde resin, JP-A-2-96163.
Esters of 1,2-diazonaphthoquinone-1-sulfonic acid and phenol / formaldehyde resin described in JP-A Nos. 2-96165 and 2-96661.
No.-5303, No.48-13854, No.48-638
No. 02, No. 48-63803, No. 48-96575
No. 49-38701, JP-B-37-18015
No., No. 41-11222, No. 45-9610, No. 4
No. 9-17481, U.S. Pat. No. 2,797,213,
No. 3,453,400, No. 3,544,323, No. 3,573,917, No. 3,674,495, No. 3,785,825, British Patent No. 1,227,602
Nos. 1,251,345 and 1,267,005
No. 1,329,888, 1,330,932
And those described in German Patent No. 854,890 are also preferably used.

In the present invention, an o-naphthoquinonediazidosulfonic acid ester compound of a polycondensation resin of polyhydroxyphenol and a ketone or aldehyde is preferably used, and these compounds are as shown below.

As the polyhydroxyphenol which is a monomer of the backbone polymer, catechol, (methyl) resorcin, hydroquinone, pyrogallol, phloroglucin and the like are preferably used. Further, more preferred is pyrogallol. As the ketone or aldehyde, acetone, formaldehyde, acetaldehyde, benzaldehyde, crotonaldehyde and the like are preferably used, and acetone is more preferable.

As a method for synthesizing a polycondensation resin of polyhydroxyphenol and ketone or aldehyde, a generally known method is applied, and polyhydroxyphenol is dissolved in ketone or aldehydes or, if necessary, an appropriate solvent. Polycondensation is performed under a suitable acid such as hydrochloric acid, phosphorus oxychloride, oxalic acid, etc. to obtain a polymer. As a polycondensation condition, a synthesis method in which a polycondensation reaction is carried out at a high temperature from the initial stage of polymerization is preferably used, as compared with a known method. For example, as a catalyst, hydrochloric acid, sulfuric acid, oxalic acid, an acid such as phosphorus oxychloride is dropped into a mixture of polyhydroxyphenol and a ketone or an aldehyde compound, a solvent used as necessary, for example, dioxane, methanol, ethanol, and aqueous tetrahydrofuran. At the same time, a formulation brought to a steady state of reflux is preferably used. The molecular weight of the polyhydroxy polymer compound obtained by these methods is 3.00 × 10 ^{2 as the} number average molecular weight Mn (polystyrene standard) determined by the GPC method.
2.00 × 10 ³ , 5.00 × 10 ³ in weight average molecular weight Mw
10 ^{2 to} 4.00 × 10 ³ are used, and more preferably M
n is 4.00 × 10 ^{2 to} 1.50 × 10 ³ , and Mw is 7.0
0 × 10 ^{2 to} 3.00 × 10 ³ , more preferably Mn is 5.
00 × 10 ^{2 to} 1.10 × 10 ³ , Mw is 8.00 × 10
^{2 to} 2.00 × 10 ³ .

When Mn is larger than 2.00 × 10 ³ and M
When using o-naphthoquinonediazidesulfonic acid ester of a polyhydroxyphenol polymer having w larger than 4.00 × 10 ³ , Mn is smaller than 3.00 × 10 ² and Mn is smaller than 5.00 × 10 ^2. Even when o-naphthoquinonediazidosulfonic acid ester of polyhydroxyphenol polymer is used, satisfactory printing durability cannot be obtained when printing is performed at high speed and under severe printing conditions such as offset rotary printing.

Preferred examples of the polyhydroxyphenol polymer which can obtain a satisfactory printing durability when printing under high-speed and severe printing conditions such as offset rotary printing are:
Resorcinol benzaldehyde resin, methylresorcinol benzaldehyde, pyrogallol / acetone resin having the above molecular weight range, more preferably pyrogallol / acetone resin. The o-naphthoquinonediazidosulfonic acid ester of these polyhydroxyphenol polymers can be easily obtained by the following synthesis method.

A polymer of polyhydroxyphenol is dissolved in an appropriate solvent, for example, dioxane, and o-naphthoquinonediazidesulfonic acid chloride is added thereto. Ethanol is easily esterified by dropwise addition of an alkali carbonate to an equivalent point. Is done.

The condensation rate of o-naphthoquinonediazide sulfonic acid chloride with respect to the OH group of this esterified product is preferably 20 to 80% (% based on one OH group), more preferably 25 to 70%, and still more preferably 30 to 80%. 60
%.

Although the molecular weight of the esterified product slightly varies depending on the condensation rate of OH groups, it is generally 20%.
For the esterified product from mol% to 70 mol%, Mn
Is 5.00 × 10 ^{2 to} 2.60 × 10 ³ and Mw is 7.00.
It is preferably from × 10 ^{2 to} 4.80 × 10 ³ , and more preferably Mn is 6.00 × 10 ^{2 to} 2.40 × 10 ³ and Mw is 9.
It is from 00 × 10 ^{2 to} 4.00 × 10 ³ . More preferably, Mn is 7.00 × 10 ^{2 to} 2.10 × 10 ³ and Mw is 1.
It is from 00 × 10 ^{3 to} 3.60 × 10 ³ . The content of the esterified compound in the photosensitive layer varies depending on the kind thereof, but is generally preferably 5 to 40% by weight, more preferably 10 to 30% by weight.

Although the o-quinonediazide compound alone forms the photosensitive layer, it is preferable to use a resin soluble in alkaline water as a binder. As the alkali-soluble resin, any resin soluble in alkaline water can be used, but a novolak resin and an alkali-soluble resin having a structural unit represented by the general formula (1) in the molecular structure of the present invention are preferable.

Resins soluble in alkaline water are used as binders, and specifically, phenol formaldehyde resins, o-, m- and p-cresol formaldehyde resins, m- / p-mixed cresols Formaldehyde resin, phenol / cresol (o
-, M-, p-, m- / p- and o- / m-). Novolak resins such as mixed formaldehyde resins, phenol-modified xylene resins, polyhydroxystyrenes, polyhalogenated hydroxystyrenes, Kaisho 5
Acrylic resins containing a phenolic hydroxyl group described in 1-334711 are exemplified.

Other suitable alkali-soluble resins have a molecular weight of 10,000-
200,000 copolymers can be mentioned.

(1) Acrylamides, methacrylamides, acrylates, methacrylates, hydroxystyrenes having an aromatic hydroxyl group;
(4-hydroxyphenyl) acrylamide, N- (4
-Hydroxyphenyl) methacrylamide, o-, m-
Or p-hydroxystyrene, o-, m- or p-hydroxyphenyl acrylate or methacrylate; (2) acrylates and methacrylates having an aliphatic hydroxyl group; 2-hydroxyethyl acrylate or methacrylate; (3) acryl Unsaturated carboxylic acids such as acid, methacrylic acid, maleic anhydride and methaconic acid (4) Methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, amyl acrylate, hexyl acrylate, cyclohexyl acrylate, acrylic acid Octyl, phenyl acrylate, benzyl acrylate, 2-chloroethyl acrylate, 4-acrylic acid
(Substituted) acrylates such as hydroxybutyl, glycidyl acrylate, N-dimethylaminoethyl acrylate, etc. (5) Methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, amyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate (Substituted) methacrylates such as octyl methacrylate, phenyl methacrylate, benzyl methacrylate, 2-chloroethyl methacrylate, 4-hydroxybutyl methacrylate, glycidyl methacrylate, N-dimethylaminoethyl methacrylate, (6) acrylamide, Methacrylamide, N-methylolacrylamide, N-methylolmethacrylamide, N-ethylacrylamide, N-ethylmethacrylamide, N-hexyl Acrylamide, N- hexyl methacrylamide, N- cyclohexyl acrylamide,
N-cyclohexylmethacrylamide, N-hydroxyethylacrylamide, N-hydroxyethylacrylamide, N-phenylacrylamide, N-phenylmethacrylamide, N-benzylacrylamide, N-benzylmethacrylamide, N-nitrophenylacrylamide, N-nitrophenyl Methacrylamide, N-ethyl-N-phenylacrylamide, N-ethyl-N-
Acrylamide or methacrylamide such as phenyl methacrylamide; (7) vinyl ethers such as ethyl vinyl ether, 2-chloroethyl vinyl ether, hydroxyethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, octyl vinyl ether, and phenyl vinyl ether; (8) vinyl acetate, vinyl chloroacetate; Vinyl esters such as vinyl butyrate and vinyl benzoate (9) Styrenes such as styrene, methyl styrene and chloromethyl styrene (10) Vinyl ketones such as methyl vinyl ketone, ethyl vinyl ketone, propyl vinyl ketone and phenyl vinyl ketone ( 11) Olefins such as ethylene, propylene, isobutylene, butadiene, isoprene, etc. (12) N-vinylpyrrolidone, N-vinyl Rubazole, 4-vinylpyridine, acrylonitrile, methacrylonitrile, etc. (13) N- (o-aminosulfonylphenyl) acrylamide, N- (m-aminosulfonylphenyl) acrylamide, N- (p-aminosulfonylphenyl) acrylamide, N Acrylamides such as-[1- (3-aminosulfonyl) naphthyl] acrylamide, N- (2-aminosulfonylethyl) acrylamide;
(O-aminosulfonylphenyl) methacrylamide,
N- (m-aminosulfonylphenyl) methacrylamide, N- (p-aminosulfonylphenyl) methacrylamide, N- [1- (3-aminosulfonyl) naphthyl] methacrylamide, N- (2-aminosulfonylethyl) methacryl Methacrylamides such as amides; o-
Unsaturated sulfonamides such as acrylates such as aminosulfonylphenyl acrylate, m-aminosulfonylphenyl acrylate, p-aminosulfonylphenyl acrylate and 1- (3-aminosulfonylphenylnaphthyl) acrylate; o-aminosulfonylphenyl methacrylate And unsaturated sulphonamides such as methacrylic esters such as m-aminosulfonylphenyl methacrylate, p-aminosulfonylphenyl methacrylate, 1- (3-aminosulfonylphenylnaphthyl) methacrylate.

Further, a copolymer obtained by copolymerizing the above-mentioned monomer and modified with glycidyl acrylate, glycidyl methacrylate or the like is also included.

These copolymers preferably contain the unsaturated carboxylic acids listed in (3), and the copolymer preferably has an acid value of 0 to 10 meq / g, more preferably 0.2 to 10 meq / g.
It is 5.0 meq / g. The preferred molecular weight of these copolymers is 10,000 to 100,000. If necessary, a polyvinyl butyral resin, a polyurethane resin, a polyamide resin, or an epoxy resin may be added to these copolymers. The alkali-soluble resin is used at 80% by weight or less of the photosensitive composition.

In the present invention, when used as a photosensitive lithographic printing plate for image formation by infrared exposure, organic acid halides and diphenyliodonium salts are preferred as acid generators from the viewpoint of storage stability and the like. As the organic halogen compound, triazines having a halogen-substituted alkyl group and oxadiazoles having a halogen-substituted alkyl group are preferable.
-Triazines are particularly preferred. Further, the maximum absorption wavelength λmax of the acid generator is preferably 200 to 350 nm,
The molar extinction coefficient ε at max is preferably 10,000 or more, particularly preferably 20,000 or more.

S- having the halogen-substituted alkyl group
As the triazine, a compound represented by the following general formula (2) is preferable.

[0046]

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In the general formula (2), R represents an alkyl group,
A halogen-substituted alkyl group, a phenylvinylene group or an aryl group (for example, a phenyl group, a naphthyl group or the like) which may be substituted with an alkoxy group, or a substituted product thereof;
X represents a halogen atom. S- represented by the general formula (2)
Examples of compounds of the triazine-based photoacid generator are shown below.

[0048]

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[0049]

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S-triazine acid generator or
44737, JP-A-9-90633, and JP-A-4
Those specifically described in JP-A-226454 can also be used.

In the present invention, one type of acid generator may be used alone or two or more types may be used in combination. The content thereof can be varied widely depending on its chemical properties and photosensitive composition or its physical properties. The amount is suitably in the range of about 0.1 to about 20% by weight, preferably 0.2 to 10% by weight, based on the total weight of the solid content of the photosensitive layer when the product is in a dry state or a photosensitive lithographic printing plate. Range.

Examples of the acid-decomposable compound usable in the present invention include JP-A-48-89003 and JP-A-51-12.
Nos. 0714, 53-133429 and 55-129
No. 95, No. 55-126236, No. 56-17345
Compounds having a C--O--C bond described in JP-A-60-37549 and compounds having a Si--O--C bond described in JP-A-60-112446; And other acid-decomposable compounds described in JP-A Nos. 60-10247. Further, compounds having a Si--N bond described in JP-A-62-222246, and compounds disclosed in JP-A-62-1251743. And orthotitanate described in JP-A-62-280841, and JP-A-62-80841.
Orthosilicate described in JP-A-280842, acetal and ketal described in JP-A-63-10153, compounds having a CS bond described in JP-A-62-244038, 63 -231
No. 442, a compound having a -OC (= O)-bond or the like can be used. Of the above, acetal and silyl ether are preferred.

The acid-decomposable compound is preferably a compound which is decomposed by the action of an acid to form a diol compound containing an ethylene glycol component or a propylene glycol component. Examples of such diol compounds include:
General formula-(CH ₂ -CH ₂ -O) _n- or-(CH ₂ -CH
Those containing a component represented by ₂ (CH ₃ ) —O) _m — are preferred. Here, n or m is preferably in the range of 1 to 5. Also,-(CH ₂ -CH ₂ -O) _n- (CH ₂ -CH ₂ (CH ₃ )-
O) Those containing a copolymer component represented by _m- are also preferable.
Examples of these diol compounds include ethylene glycol, diethylene glycol, triethylene glycol,
Tetraethylene glycol, pentaethylene glycol, polyethylene glycol, propylene glycol,
Dipropylene glycol, tripropylene glycol,
Examples include tetrapropylene glycol, pentapropylene glycol, polypropylene glycol, and poly-ethylene glycol-propylene glycol copolymer.
Ethylene glycol and diethylene glycol are particularly preferred from the viewpoint of sensitivity and development stability. Further, acetal or silyl ether containing these diol components is particularly preferable.

Acetals are preferably synthesized from the condensation of the diol compound with the dimethyl acetal or diethyl acetal of aldehydes and ketones from the viewpoint of yield.

Particularly preferred are aldehyde or ketone components having a solubility in water at 25 ° C. of 1 to 100 g / l. If the amount is less than 1 g / l, sludge is likely to be generated in the continuous processing, and if it is more than 100 g / l, the resolution of the formed image tends to decrease. Specific examples include benzaldehyde, 4-hydroxybenzaldehyde, 3,4
-Dihydroxybenzaldehyde, 2-pyridinecarbaldehyde, piperonal, furaldehyde, terephthalaldehyde, 5-methyl-2-furaldehyde, phenoxyacetaldehyde, phenylacetaldehyde, cyclohexanecarbaldehyde, vanillin, cyclohexanone, cyclohexen-1one, isobutyraldehyde, pentanal And the like. Of these, cyclohexanone is the most stable and preferred in continuous processing.

The silyl ethers are synthesized by condensation of a silyl compound with the diol compound. Specific examples of the silyl compound include dichlorodimethylsilane, dichlorodiethylsilane, methylphenyldichlorosilane, diphenyldichlorosilane, and methylbenzyldichlorosilane. The solubility of the silyl compound formed by decomposition under the action of an acid in water at 25 ° C. is 1 to 100 g / l.
Are preferred.

Acetals and silyl ethers may be co-condensed with other alcohol components in addition to the diol compounds. Specific examples of the alcohol component include substituted or unsubstituted monoalkyl alcohols such as methanol, ethanol, n-propanol, isopropanol, butanol, pentanol, hexanol, cyclohexanol, and benzyl alcohol; ethylene glycol monomethyl ether; Examples thereof include glycol ether alcohols such as ethyl ether, ethylene glycol monophenyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, and diethylene glycol monophenyl ether, and substituted or unsubstituted polyethylene glycol alkyl ethers and polyethylene glycol phenyl ethers. Further, as the dihydric alcohol, for example, pentane-1,5-diol, n-hexane-
1,6-diol, 2-ethylhexane-1,6-diol, 2,3-dimethyl-hexane-1,6-diol, heptane-1,7-diol, cyclohexane-
1,4-diol, nonane-1,7-diol, nonane-1,9-diol, 3,6-dimethyl-nonane-1,
9-diol, decane-1,10-diol, dodecane-1,12-diol, 1,4-bis- (hydroxymethyl) -cyclohexane, 2-ethyl-1,4-bis-
(Hydroxymethyl) -cyclohexane, 2-methyl-
Cyclohexane-1,4-diethanol, 2-methyl-
Cyclohexane-1,4-dipropanol, thio-dipropylene glycol, 3-methylpentane-1,5-diol, dibutylene-glycol, 4,8-bis- (hydroxymethyl) -tricyclodecane, 2-butene-
1,4-diol, p-xylylene glycol, 2,5
-Dimethyl-hex-3-yne-2,5-diol, bis- (2-hydroxyethyl) -sulfide, 2,
2,4,4, -tetramethylcyclobutane-1,3-diol and the like.

The preferred molecular weight range of the above-mentioned acetal or silyl ether containing a diol component is GPC.
Weight average molecular weight M measured in terms of polystyrene
w is 500 to 10000, preferably 1000 to 300
0.

The preferred content of the acid-decomposable compound in the layer of the photosensitive composition is 5 to 50%, more preferably 10 to 50%.
３０30%. Above this level, the sensitivity decreases, and below this level, the image forming ability decreases.

As the infrared absorbing dye that can be used in the present invention, a compound that absorbs light having a wavelength of 700 to 1500 nm is used. For example, it is preferable to use an infrared absorbing dye having absorption at a wavelength of 700 nm or more, carbon black, magnetic powder, or the like. Particularly preferred infrared absorbing dyes are dyes having a maximum absorption at 700 to 1200 nm and a peak molar extinction coefficient ε of 105 or more.

Examples of the infrared absorbing dye include a cyanine dye, a squarium dye, a croconium dye, an azurenium dye, a phthalocyanine dye, a naphthalocyanine dye, a polymethine dye, a naphthoquinone dye,
Thiopyrylium dyes, dithiol metal complex dyes, anthraquinone dyes, indoaniline metal complex dyes,
And intermolecular CT dyes. In the present invention, as the infrared absorbing dye, a cyanine dye is particularly preferable,
Specific examples of the cyanine dye are shown below, but the present invention is not limited thereto.

[0062]

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[0063]

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[0064]

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[0065]

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The infrared absorbing dye is 750 to 900 nm when a semiconductor laser is used as a light source for image exposure,
900 to 1200 nm when using a YAG laser
And those having a molar extinction coefficient of ε> 1 × 10 ⁵ are preferred. Further, one or more dyes belonging to both systems may be used in combination.

These dyes can be synthesized by known methods, but the following commercially available products can also be used.

Nippon Kayaku: IR750 (anthraquinone type); IR002, IR003 (aluminum type);
R820 (polymethine type); IRG022, IRG03
3 (diimmonium-based); CY-2, CY-4, CY-
9, CY-20, Mitsui Toatsu: KIR103, SIR10
3 (phthalocyanine); KIR101, SIR114
(Anthraquinone type); PA1001, PA1005
PA1006, SIR128 (metal complex type), Dainippon Ink & Chemicals: Fastogen blue 8120, Midori Kagaku: MIR-101, 1011, 1021 and the like. In addition, it is also commercially available from various companies such as Nippon Kogaku Dye, Sumitomo Chemical, Fuji Photo Film and the like.

In the present invention, the amount of the infrared absorber added is preferably in the range of 0.5 to 10% by weight. If the amount exceeds 10% by weight, the developability of the non-image area (exposed area) decreases, and if it is less than 0.5% by weight, the sensitivity decreases.

The photosensitive composition of the present invention can significantly improve the printing durability when used as a lithographic printing plate by having a pigment. Examples of the pigment include known organic and inorganic pigments, and the pigments described in “Coloring Material Engineering Handbook” by Asakura Shoten and “Pigment Handbook” by Seibundo Shinkosha can be used without any particular limitation. Further, in order to obtain visible image after development, the pigment is preferably colored, and more preferably a high density is obtained. In that respect, it is preferable that the pigment is selected from phthalocyanine and carbon black not only to improve the printing durability but also to obtain a visible image after development.

In the present invention, it is preferable to use a compound which is insolubilized with an acid. Examples of the compound insolubilized with an acid that can be used in the present invention include a silanol compound,
Compounds containing carboxylic acids or carboxylic acid derivatives and compounds having hydroxyl groups, compounds having cationic double bonds, secondary or tertiary alcohols having aromatic groups, methylol groups, alkoxymethyl groups or acetoxymethyl groups An alkali-soluble polymer having an aromatic ring in the molecule is exemplified.

The silanol compound has, on average, one or more hydroxyl groups bonded to silicon atoms per silicon atom. Here, the average means that, for example, even if a compound has one silicon atom to which no hydroxyl group is bonded, the same effect can be obtained if one silicon atom to which two hydroxyl groups are bonded is obtained. is there. As such a silanol compound, for example,
Diphenylsilanediol, triphenylsilanol,
Cis- (1,3,5,7-tetrahydroxy) -1,
3,5,7-tetraphenylcyclotetrasiloxane or the like can be used.

The amount of the silanol compound is 5 to 70% by weight.
Is preferably within the range.

Examples of the carboxylic acid or carboxylic acid derivative include aromatic carboxylic acids such as cinnamic acid, benzoic acid, tolylacetic acid, toluic acid and isophthalic acid; aromatic esters such as dimethyl isophthalate and di-t-butyl isophthalate;
Acid anhydrides such as glutaric anhydride, succinic anhydride and benzoic anhydride, styrene-maleic anhydride copolymer, styrene
Copolymers such as methacrylic acid copolymer are exemplified.

As the compound having a hydroxyl group,
Polyhydric alcohols such as glycerin, poly p-hydroxystyrene, p-hydroxystyrene / styrene copolymer,
High molecular compounds such as novolak resins are exemplified.

The composition ratio of the carboxylic acid or its derivative to the compound having a hydroxyl group is 1:30 to 30 in equivalent ratio.
It is preferably in the range of 1 to 1.

One of the compound having a hydroxyl group and the carboxylic acid or a derivative thereof may be a polymer compound. When the compound having a hydroxyl group is a polymer compound, it is preferable to use a carboxylic acid or a derivative thereof in an amount of 1 to 50 in a weight ratio to the polymer compound 100. When the carboxylic acid or its derivative is a polymer compound, it is preferable to use a compound having a hydroxyl group with respect to the polymer compound 100 in an amount of 1 to 20 by weight ratio.

From the viewpoint of coatability, at least one of the carboxylic acid and the compound having a hydroxyl group is preferably a high molecular compound. However, even if both are low molecular weight, it is sufficient that the coating film can be formed by a method such as mixing a high molecular compound.

Further, a high molecular compound having both a compound having a hydroxyl group and a carboxylic acid or a carboxylic acid derivative can be used. Examples of the polymer compound include p-hydroxystyrene having a hydroxyl group and a carboxylic acid or a carboxylic acid derivative, such as methacrylic acid ester such as methyl methacrylate, acrylic acid ester such as methyl acrylate, maleic anhydride, methacrylic acid, and acrylic acid. And the like.

The weight average molecular weight of these high molecular compounds is preferably in the range of 1,000 to 50,000. If the molecular weight is less than 1,000, sufficient heat resistance and coating properties cannot be obtained. On the other hand, if the molecular weight exceeds 50,000, the solubility in an aqueous alkali solution is not sufficient, and pattern deformation due to swelling is observed, so that high resolution cannot be obtained.

The amounts of the carboxylic acid or its derivative and the compound having a hydroxyl group are preferably in the range of 5 to 50% by weight.

Compounds having a cationically polymerizable double bond include p-diisopropenylbenzene, m-diisopropenylbenzene, diphenylethylene, indenone, acenaphthene, 2-norbornene, 2,5-norbornadiene, 2,3- Benzofuran, indole, 5-
Examples include at least one compound selected from the group consisting of methoxyindole, 5-methoxy-2-methylindole, N-vinyl-2-pyrrolidone, and N-vinylcarbazole.

The amount of the compound having a cationic double bond is preferably in the range of 5 to 50% by weight.

Examples of the secondary or tertiary alcohol having an aromatic group include biphenyl derivatives, naphthalene derivatives and triphenyl derivatives.

As specific compounds, for example, 4,4 '
-Bis (α-hydroxyisopropyl) biphenyl,
3,3'-bis (α-hydroxyisopropyl) biphenyl, 2,4,2 ', 4'-tetra (α-hydroxyisopropyl) biphenyl, 3,5,3', 5'-tetra (α-hydroxyisopropyl) Biphenyl, 4,4 '
-Bis (α-hydroxyisopropyl) biphenyl sulfone, 3,3′-bis (α-hydroxyisopropyl)
Biphenyl sulfone, 4,4'-bis (α-hydroxyisopropyl) biphenylmethane, 3,3'-bis (α
-Hydroxyisopropyl) biphenylmethane, 4,
4'-bis (α-hydroxyisopropyl) biphenyl sulfide, 3,3'-bis (α-hydroxyisopropyl) biphenyl sulfide, 2,2-bis (4-α-
Hydroxyisopropylphenyl) propane, 2,2-
And bis (3-α-hydroxyisopropylphenyl) propane. The naphthalene derivative is 1,5-bis (1
-Hydroxypropyl) naphthalene, 2,6-bis (α
-Hydroxypropyl) naphthalene and the like. Triphenyl derivatives are tris (4-α-hydroxyisopropylphenyl) methane, tris (3-α-hydroxyisopropylphenyl) methane, 1,1,1-tris (4-
α-hydroxyisopropylphenyl) ethane, 1,
1,1-tris (3-α-hydroxyisopropylphenyl) ethane and the like.

The secondary or tertiary alcohol having a hydroxyl group at the carbon directly bonded to the aromatic ring includes a phenylmethanol derivative, an alicyclic alcohol having an aromatic ring, and the like.

The phenylmethanol derivatives include:
For example, diphenylmethanol, 4,4'-difluorodiphenylmethanol, 4,4'-dichloro-diphenylmethanol, 4,4'-dimethyl-diphenylmethanol, 4,4'-dimethoxydiphenylmethanol, triphenylmethanol, α- (4 -Pyridyl) -benzhydrol, benzylphenylmethanol, 1,1-diphenylethanol, cyclopropyldiphenylmethanol, 1-phenylethyl alcohol, 2-phenyl-2
-Propanol, 2-phenyl-2-butanol, 1-
Phenyl-1-butanol, 2-phenyl-3-butyn-2-ol, 1-phenyl-1-propanol, 1,
2-diphenylethylene glycol, tetraphenylethylene glycol, 2,3-diphenyl-2,3-butanediol, α-naphtholbenzein, α, α′-dihydroxy-p-diisopropylbenzene, α, α′-
Dihydroxy-m-diisopropylbenzene and the like.

The alicyclic alcohol having an aromatic ring includes 1-indanol, 2-bromoindanol,
Chromanol, 9-fluorenol, 9-hydroxy-
3-fluorene, 9-hydroxyxanthene, 1-acenaphthenol, 9-hydroxy-3-nitrofluorene, thiochroman-4-ol, 9-phenylxanthen-9-ol, 1,5-dihydroxy-1,2,3 ,
4-tetrahydronaphthalene, dibenzosuberenol,
Dibenzosuberol and the like.

Further, in addition to the above, 1- (9-anthryl) ethanol, 2,2,2
Examples thereof include 2-trifluoro-1- (9-anthryl) ethanol and 1-naphthylethanol.

The alkali-soluble polymer having an aromatic ring having a methylol group, an alkoxymethyl group or an acetoxymethyl group in the molecule includes vinylbenzyl alcohol, α-methylvinylbenzyl alcohol, vinylbenzyl acetate, α-methylvinylbenzyl acetate, It is preferable to copolymerize with monomers such as p-methoxystyrene and 4-methylolphenyl methacrylamide.

The aluminum plate used in the present invention contains pure aluminum or aluminum as a main component.
It is a plate-like body such as an aluminum alloy containing a trace amount of foreign atoms. This heteroatom includes silicon, iron, manganese, copper, magnesium, chromium, zinc, bismuth, nickel, titanium and the like. The content of foreign atoms in the alloy is at most 10% by weight or less. Aluminum which is suitable for the present invention is pure aluminum. However, since pure aluminum is difficult to produce due to refining technology, it is preferable that the content of foreign atoms be as low as possible. In addition, any aluminum alloy having the above-described content can be said to be a material applicable to the present invention. As described above, the composition of the aluminum plate applied to the present invention is not specified, and conventionally known and publicly available materials can be appropriately used. The thickness of the aluminum plate used in the present invention is approximately 0.1 mm to
It is about 0.5 mm.

Prior to the surface roughening treatment of the aluminum plate, if necessary, a degreasing treatment with, for example, a surfactant or an alkaline aqueous solution is performed to remove the rolling oil on the surface.

The photosensitive lithographic printing plate of the present invention may be one that can be used on one side only, or one that can be used on both sides by the same treatment. Since the same applies to both surfaces, the case of one surface will be described below.

Examples of the surface roughening method include a method of mechanically roughening the surface, a method of electrochemically dissolving the surface, and a method of chemically selectively dissolving the surface. As a method for mechanically roughening the surface, a known method called a ball polishing method, a brush polishing method, a blast polishing method, a buff polishing method, or the like can be used. Further, as an electrochemical surface roughening method, there is a method of performing an alternating or direct current in a hydrochloric acid or nitric acid electrolyte. Further, as disclosed in JP-A-54-63902, a method in which both are combined can be used.

The aluminum plate thus roughened is subjected to an alkali etching treatment and a neutralization treatment as required.

As the electrolyte used for the anodic oxidation treatment of the aluminum plate, any electrolyte can be used as long as it forms a porous oxide film.
Phosphoric acid, oxalic acid, chromic acid or a mixed acid thereof is used, and the concentration of the electrolyte is appropriately determined depending on the type of the electrolyte.

The conditions of the anodizing treatment vary depending on the electrolyte to be used and cannot be specified unconditionally. However, in general, the concentration of the electrolyte is 1 to 80% by weight, the solution temperature is 5 to 70 ° C., and the current density is 5 to 70%. 60A / dm ^2, voltage 1 to 100 V, is suitable if the electrolysis time of 10 seconds to 50 minutes.

[0098] The amount of the anodized film is at 1.0 g / m ² or more, more preferably in the range of 2.0 to 6.0 g / m ^2. When the amount of the anodic oxide film is less than 1.0 g, the printing durability is insufficient, and the non-image area of the lithographic printing plate is easily damaged, and the ink is attached to the damaged area during printing, so-called “scratch stain”. Is more likely to occur.

The aluminum plate may be optionally coated with an inorganic undercoat layer (intermediate layer) such as an alkali metal silicate described in US Pat. No. 3,181,461 before coating the photosensitive layer.
And the hydrophilic celluloses described in U.S. Pat. No. 1,860,426, the amino acids and salts thereof described in JP-A-60-149491, JP-A-63-165183, and JP-A-60-232998. And amines having a hydroxyl group and salts thereof described in JP-A-62-1949.
No. 4, the phosphate described in JP-A-59-101651.
An organic undercoat layer (intermediate layer) such as a polymer compound containing a monomer unit having a sulfo group described in JP-A-6-135175 or a compound described in JP-A-6-135175 is provided. As the undercoat layer, other than those described above, those conventionally known can be used.

Further, in order to prevent abrasion of the photosensitive layer when the photosensitive lithographic printing plates are stacked, and to prevent elution of the aluminum component into the developing solution during development, a protective layer is provided on the back surface of the support. Provided processing can be performed.

[0101]

EXAMPLES Example 1 An aluminum plate having a thickness of 0.24 mm (JIS 1050,
The surface of the heat-treated H16) was immersed in a 10% by weight aqueous sodium hydroxide solution at 50 ° C. for 20 seconds to perform a degreasing treatment, washed with water, neutralized with 10% sulfuric acid, and further washed with water.

Then, this aluminum plate was suspended in 20% by weight of an abrasive (alumina # 800) in water, and a supply amount of 20% was added.
l / min, brush rotation speed 240 rpm, conveyance speed 2.0 m / min, mechanical surface roughening by brush polishing, washing with water, and then in a 6% sodium hydroxide aqueous solution kept at 85 ° C. for 20 seconds. After immersion, it was washed with water, immersed in a 10% sulfuric acid aqueous solution kept at 25 ° C. for 5 seconds, subjected to desmut treatment, and washed with water. This aluminum plate is then
In a 10 g / liter hydrochloric acid aqueous solution, at a temperature of 30 ° C. and a distance between the electrodes of 9 mm, a current density of 25 was obtained using a sine wave alternating current.
A / dm ² , an electrochemical surface treatment was performed at an electric quantity of 150 C / dm ² , washed with water, immersed in a 1% aqueous solution of sodium hydroxide kept at 50 ° C. for 20 seconds, washed with water, and then washed with 25 ° C. It was immersed in a maintained 10% sulfuric acid aqueous solution for 5 seconds, subjected to a desmut treatment, washed with water, and adjusted to a thickness of 2.7 g / m ² at a current density of 2 A / dm ² in a 20 wt% H ₂ SO ₄ aqueous solution. The support (1) was prepared by anodizing.

Each of the following compounds (a) to (e) was mixed with the following photosensitive solution A on the support (1), applied using a wire bar, dried at 100 ° C. for 1 minute, and then each photosensitive lithographic printing plate. Samples 1 to 5 were obtained. The application amount after drying is about 1.8
g / m ² .

Photosensitive solution A Esterified product of 1,2-diazonaphthoquinone-5-sulfonyl chloride and pyrogallol-acetone resin (described in Example 1 of US Pat. No. 3,635,709) 2.41 g Cresol-formaldehyde novolak resin 3.89 g (meta / para ratio; 6: 4, MW 4000) Alkali-soluble resin of the present invention (Exemplified compound 1-16) 0.20 g Acid generator (Exemplified compound 2-1) 0 0.046 g Victoria Pure Blue BOH (manufactured by Hodogaya Chemical Co., Ltd.) 0.062 g Megafac F-177 0.023 g (fluorosurfactant manufactured by Dainippon Ink and Chemicals, Inc.) Polyethylene glycol # 2000 0.046 g Methyl ethyl ketone 9 g Methyl lactate 35 g Additional compounds (ae) 0.33 g.

The additive compounds and the samples prepared by the addition are as follows.

(A) Phenylphosphonic acid (photosensitive lithographic printing plate sample 1) (b) Ethylphosphonic acid (photosensitive lithographic printing plate sample 2) (c) Diethylphosphinic acid (photosensitive lithographic printing plate sample 3) (d) ) Phenylphosphinic acid (photosensitive lithographic printing plate sample 4) (e) Methylene diphosphonic acid (photosensitive lithographic printing plate sample 5) For comparison, polyvinylphosphonic acid (weight average molecular weight 3,000) was dissolved in methanol. The support (1) was provided on the support (1) such that the coating amount after drying was 30 mg / m ² , the support (2) was prepared, and the photosensitive solution A was applied using a wire bar, and the coating was performed at 100 ° C. for 1 minute. It dried and the photosensitive lithographic printing plate sample 6 was obtained. The coated amount after drying was about 1.8 g / m ² .

Further, for comparison, 0.33 g of tetrahydrophthalic anhydride compound was mixed with the above-mentioned photosensitive solution A on the support (1), and the mixture was applied using a wire bar.
After drying for 5 minutes, a photosensitive lithographic printing plate sample 7 was obtained. The coated amount after drying was about 1.8 g / m ² .

The photosensitive lithographic printing plate thus produced was passed through a transparent positive film in a vacuum frame to obtain a photosensitive lithographic printing plate.
m from a distance of 4 m by a metal halide lamp of 4 kW
After exposure for 0 seconds, development was performed at 25 ° C. for 45 seconds with a 6-fold diluted solution of a developing solution (SDR-1, manufactured by Konica Corporation).

After development as described above, the plate was washed sufficiently with water, gummed, and printed by a conventional procedure. Table 1 shows the results of the stain and the printing durability of the non-image portion and the remaining color of the non-image portion on the plate.

[0110]

[Table 1]

From the results shown in Table 1, it can be seen that the photosensitive lithographic printing plate according to the present invention satisfies all of the remaining colors in the non-image area, stains during printing, and printing durability as compared with the comparative example. I understand.

Example 2 The following compounds (a) to (e) were mixed with the following photosensitive solution B on a support (1), and the mixture was applied using a wire bar.
Dry at 0 ° C. for 1 minute to obtain a photosensitive lithographic printing plate sample 8
~ 12 were obtained. The coated amount after drying was about 1.8 g / m ² .

Photosensitive solution B 7.00 g of a novolak resin obtained by co-condensing phenol, m-, p-mixed cresol and formaldehyde (Mw = 4000, molar ratio of phenol / m-cresol / p-cresol respectively. 5/57/38) Alkali-soluble resin of the present invention (Exemplified compound 1-18) 0.50 g Acid-decomposable compound A (Synthesis method is shown below) 2.00 g Acid generator (Exemplified compound 2-12) 30 g Infrared absorbing dye (exemplified compound IR16) 0.10 g Crystal violet 0.03 g Fluorinated surfactant S-381 (manufactured by Asahi Glass Co., Ltd.) 0.05 g Methyl lactate 70.0 g Methyl ethyl ketone 20.0 g Synthesis of acid-decomposable compound A 1.0 mol of 1,1-dimethoxycyclohexane, 1.0 mol of diethylene glycol and p-toluenesulfonic acid Hydrate 0.003 mole, reacted for 1 hour at 100 ° C. with stirring toluene 500 ml, then gradually raising the temperature to 0.99 ° C., was reacted for 4 hours at further 0.99 ° C.. Methanol generated by the reaction was distilled off during this period. After cooling, the reaction product was sufficiently washed with water, and sequentially washed with a 1% aqueous NaOH solution and a 1N aqueous NaOH solution. The extract was washed with brine, dried over anhydrous potassium carbonate, and concentrated under reduced pressure. It was dried for 10 hours while heating to 80 ° C. under vacuum to obtain a wax-like compound. The weight average molecular weight Mw in terms of polystyrene measured by GPC was about 1600.

For comparison, polyvinyl phosphonic acid (weight average molecular weight: 3,000) was dissolved in methanol.
The support (1) was provided on the support (1) so that the coating amount after drying was 30 mg / m ² , the support (2) was prepared, and the photosensitive solution B was applied using a wire bar, and dried at 100 ° C. for 1 minute. Thus, a photosensitive lithographic printing plate sample 13 was obtained. The coated amount after drying was about 1.8 g / m ² .

Further, for comparison, only the photosensitive solution B was applied to the support (1) using a wire bar, and
It dried at 1 degreeC for 1 minute, and obtained the photosensitive lithographic printing plate sample 14.
The coated amount after drying was about 1.8 g / m ² .

The photosensitive lithographic printing plate thus produced was exposed at an exposure energy of 150 mJ / cm ² by an exposure machine (Trendsetter 3244; semiconductor laser output: 10 W, 240 channel machine) manufactured by Cleo Products Co., Ltd.
Developing was performed at 25 ° C. for 45 seconds with a 6-fold diluted solution of a developing solution (SDR-1, manufactured by Konica Corporation).

After development as described above, washing was carried out sufficiently, gumming was performed, and printing was performed in a conventional manner. Table 2 shows the results of the stain and printing durability of the non-image portion and the remaining color of the non-image portion on the plate.

[0118]

[Table 2]

From the results shown in Table 2, it can be seen that the photosensitive lithographic printing plate according to the present invention satisfies all of the remaining colors in the non-image area, stains during printing, and printing durability as compared with the comparative example. I understand.

[0120]

According to the present invention, it is possible to provide a photosensitive composition and a photosensitive lithographic printing plate which are excellent in the residual color of the non-image area, the stain during printing, and the printing durability.

Claims (4)

[Claims] 1. A photosensitive composition comprising at least one compound selected from compounds represented by the following general formula (I) or (II). General formula (I) R ¹ (PO (OH) ₂ ) _n General formula (II) R ¹ (PO (OH) (R ² )) _n [wherein n is 1 or 2 and n is 1 , R ¹ ,
R ² is a substituted or unsubstituted alkyl group, alkoxy group,
Represents an aryloxy group, an aryl group, an acyl group, or an acyloxy group; when n is 2, R ¹ represents a substituted or unsubstituted alkylene group or an arylene group; and R ² represents a substituted or unsubstituted alkyl group, an alkoxy group, an aryloxy group. Represents an aryl group, an acyl group, or an acyloxy group. ] 2. The photosensitive composition according to claim 1, wherein the compound represented by the general formula (I) or (II) is contained in an amount of 0.1 to 20% by weight with respect to the photosensitive composition. A photosensitive composition comprising: an alkali-soluble resin having the following structural unit in a molecular structure; and an o-quinonediazide compound. Embedded image Wherein R ₁ and R ₂ are a hydrogen atom, an alkyl group or a carboxyl group, R ₃ is a hydrogen atom, a halogen atom or an alkyl group, R ₄ is a hydrogen atom, an alkyl group, a phenyl group or an aralkyl group, and A is a nitrogen atom And m represents 0 or 1, and B represents a phenylene group which may have a substituent or a naphthylene group which may have a substituent. ] 3. The composition according to claim 1, wherein the compound represented by the general formula (I) or (II) is contained in an amount of 0.1 to 20% by weight based on the weight of the photosensitive composition, and further contains an infrared absorbent. The photosensitive composition according to claim 1, characterized in that: 4. The aluminum support according to claim 1, wherein the aluminum support is subjected to a surface roughening treatment, followed by anodic oxidation, and the anodic oxide film layer is 1.0 g / m ² or more. A photosensitive lithographic printing plate comprising a photosensitive composition.